Observation of inter-grain Josephson effects in Y-Ba-Cu-O samples

Josephson effects have been observed in bulk samples of Y-Ba-Cu-O. The magnitude of the zero-voltage current is found to change systematically with externally applied small magnetic fields of a few mG. It is also found to vary when samples are irradiated with microwaves. These observations suggest the presence of inter-grain Josephson junctions.     

Effect of macropore convection on mass transfer in a bidisperse adsorbent particle

The importance of adsorption induced convection in the macropores of a bidisperse adsorbent particle is studied for a step change in mole fraction or total pressure at the surface of the particle. Material balance equations for a binary gas mixture are written for both the macropores and the macropores with allowance for convection in the macropores, which is described by Darcy's law. The coupled set o1' partial differential equations is solved by orthogonal collocation. The enhancement in mass transfer as a result of convection is assessed by comparing the fractional uptake curves obtained with and without allowance for convection. Both equilibrium-based and kinetic-based separation processes are considered. The effect of the presence of convection in determining the controlling diffusional resistance (macropore or micropore) is also examined. Due to inclusion of convection no single non-dimensional group alone can determine the relative importance of macropore and micropore resistances. Results show that convection can significantly affect the performance of an equilibrium-based macropore diffusion controlled process and that the enhancement in mass transfer is more for a particle with a high value of Darcy permeability.     

Joule heating in packed capillaries used in capillary electrochromatography

Effective heat dissipation is critical for reproducible and efficient separations in electrically driven separation systems. Flow rate, retention kinetics, and analyte diffusion rates are some of the characteristics that are affected by variation in the temperature of the mobile phase inside the column. In this study, we examine the issue of Joule heating in packed capillary columns used in capillary electrochromatography (CEC). As almost all commonly used CEC packings are poor thermal conductors, it is assumed that the packing particles do not conduct heat and heat transfer is solely through the mobile phase flowing through the system. The electrical conductivity of various mobile phases was measured at different temperatures by a conductivity meter and the temperature coefficient for each mobile phase was calculated. This was followed by measurement of the electrical current at several applied voltages to calculate the conductivity of the solution within the column as a function of the applied voltage. An overall increase in the conductivity is attributed to Joule heating within the column, while a constant conductivity means good heat dissipation. A plot of conductivity versus applied voltage was used as the indicator of poor heat dissipation. Using theories that have been proposed earlier for modeling of Joule heating effects in capillary electrophoresis (CE), we estimated the temperature within CEC columns. Under mobile and stationary phase conditions typically used in CEC, heat dissipation was found to be not always efficient. Elevated temperatures within the columns in excess of 23 degrees C above ambient temperature were calculated for packed columns, and about 35 degrees C for an open column, under a given set of conditions. The results agree with recently published experimental findings with nuclear magnetic resonance (NMR) thermometry, and Raman spectroscopic measurements.     

Isolable acetylene complexes of copper and silver

Copper and silver play important roles in acetylene transformations but isolable molecules with acetylene bonded to Cu(i) and Ag(i) ions are scarce. This report describes the stabilization of π-acetylene complexes of such metal ions supported by fluorinated and non-fluorinated, pyrazole-based chelators. These Cu(i) and Ag(i) complexes were formed readily in solutions under an atmosphere of excess acetylene and the appropriate ligand supported metal precursor, and could be isolated as crystalline solids, enabling complete characterization using multiple tools including X-ray crystallography. Molecules that display κ²-or κ³-ligand coordination modes and trigonal planar or tetrahedral metal centers have been observed. Different trends in coordination shifts of the acetylenic carbon resonance were revealed by ¹³C NMR spectroscopy for the Cu(i) and Ag(i) complexes. The reduction in acetylene _{C C} due to metal ion coordination is relatively large for copper adducts. Computational tools were also used to quantitatively understand in detail the bonding situation in these species. It is found that the interaction between the transition metal fragment and the acetylene ligand is significantly stronger in the copper complexes, which is consistent with the experimental findings. The C C distance of these copper and silver acetylene complexes resulting from routine X-ray models suffers due to incomplete deconvolution of thermal smearing and anisotropy of the electron density in acetylene, and is shorter than expected. A method to estimate the C C distance of these metal complexes based on their experimental _{C C} is also presented.

Gaseous acetylene can be trapped on copper(i) and silver(i) sites supported by pyrazole-based scorpionates to produce isolable molecules for detailed investigations and the study of metal-acetylene bonding.     

Pressure induced phase transitions in Ga1 − x In x P

We have theoretically investigated the effect of pressure on the structural stability of GaP?:?InP mixed system. The three-body-potential (TBP) model has been used. The TBP model consists of long-range as well as short-range interactions; the long-range part includes the modified Coulomb force as well as a three-body term; the short-range part in TBP defines the van der Waals and overlap repulsive interactions. We observe a pressure-induced structural phase transformation from ZnS (B3) to NaCl (B1) type phase in Ga _1?x In _x P. Our calculated transition pressures for the initial GaP and final InP compound semiconductors are in good agreement with other reported data.     

Electrochemical studies of novel olivine-layered (LiFePO4-Li2MnO3) dual composite as an alternative cathode material for lithium-ion batteries

Journal of Solid State Electrochemistry - In the present work, olivine-layered composites, i.e., LiFePO4-Li2MnO3, are successfully synthesized in the form of a single monolithic electrode and layer...     

Effect of ionic liquid on polyaniline chemically synthesised under falling-pH conditions

This study investigates the effect of the ionic liquid 1-butyl-3-methyl imidazolium chloride ([bmim]Cl) on the morphological, structural, and electronic properties of polyaniline (PANI) products synthesised by the falling-pH method. Products were characterised by SEM, FT-IR, UVVIS, N₂-physisorption, and conductivity measurements. The [bmim]Cl addition strongly influenced the PANI morphology, specific surface area, porosity, and conductivity. Depending on the [bmim]Cl: ANI ratio and the synthesis pH, a wide range of PANI nanostructures could be prepared, with rod-like, and fibre-like elongated structures being the dominant morphology under most experimental conditions. Samples prepared in the presence of [bmim]Cl exhibit specific areas of ca 22–35 m² g^?1. The conductivity of the final products depends on the [bmim]Cl: ANI ratio. Temperature dependence of conductivity in the temperature range from 77 K to 300 K was also studied.     

Regioselective Synthesis and Photophysical and Electrochemical Studies of 20‐Substituted Cyanine Dye–Purpurinimide Conjugates: Incorporation of NiII into the Conjugate Enhances its Tumor‐Uptake and Fluorescence‐Imaging Ability

We report herein a simple and efficient approach to the synthesis of a variety of meso‐substituted purpurinimides. The reaction of meso ‐ substituted purpurinimide with N‐bromosuccinimide regioselectively introduced a bromo functionality at the 20‐position, which on further reaction with a variety of boronic acids under Suzuki reaction conditions yielded the corresponding meso‐substituted analogues. Interestingly, the free base and the metalated analogues showed remarkable differences in photosensitizing efficacy (PDT) and tumor‐imaging ability. For example, the free‐base conjugate showed significant in vitro PDT efficacy, but limited tumor avidity in mice bearing tumors, whereas the corresponding Ni^II derivative did not produce any cell kill, but showed excellent tumor‐imaging ability at a dose of 0.3 μmol kg^?1 at 24, 48, and 72 h post‐injection. The limited PDT efficacy of the Ni^II analogue could be due to its inability to produce singlet oxygen, a key cytotoxic agent required for cell kill in PDT. Based on electrochemical and spectroelectrochemical data in DMSO, the first one‐electron oxidation (0.52 V vs. SCE) and the first one‐electron reduction (?0.57–0.67 V vs. SCE) of both the free base and the corresponding Ni^II conjugates are centered on the cyanine dye, whereas the second one‐electron reduction (?0.81 V vs. SCE) of the two conjugates is assigned to the purpurinimide part of the molecule. Reduction of the cyanine dye unit is facile and occurs prior to reduction of the purpurinimide group, which suggests that the cyanine dye unit as an oxidant could be the driving force for quenching of the excited triplet state of the molecules. An interaction between the cyanine dye and the purpurinimide group is clearly observed in the free‐base conjugate, which compares with a negligible interaction between the two functional groups in the Ni^II conjugate. As a result, the larger HOMO–LUMO gap of the free‐base conjugate and the corresponding smaller quenching constant is a reason to decrease the intramolecular quenching process and increase the production of singlet oxygen to some degree.     

Supercritical Fluid Extract of Putranjiva roxburghii Wall. Seeds Mitigates Fertility Impairment in a Zebrafish Model

Putrajeevak (Putranjiva roxburghii Wall.; synonym Drypetes roxburghii (Wall.) Hurus) seeds have been used since ancient times in the treatment of infertility in the Ayurvedic system of medicine in India. In this study, the oil component of Putrajeevak seeds (PJSO) was extracted using the supercritical fluid extraction (SCFE) method using liquid CO₂ and the constituents were analyzed using gas chromatography-flame ionized detectorand high-performance thin-layer chromatography. PJSO contained trace amounts of β-sitosterol with oleic and linoleic acids as the major fatty acid constituents. Male and female zebrafish were mutagenized with N-ethyl-N-nitrosourea (ENU) and fish that produced less than 20 viable embryos were selected for the study. SCFE oil extracts from the P. roxburghii seeds were used in this study to reverse fertility impairment. The mutant fish were fed with PJSO for a period of 14 days and the rates of fertility, conception, and fecundity were determined with wild-type healthy fish as a breeding partner. Treatment with PJSO increased the ovarian follicle count as well as the number of mature eggs, while reducing the number of ovarian cysts. Sperm count as well as sperm motility were greatly enhanced in the ENU-mutagenized male zebrafish when treated with PJSO. The results obtained in this study demonstrate the effectiveness of P. roxburghii seed oil in reversing impaired fertility in both male and female zebrafish models.     

Evanescent tunneling of an effective surface plasmon excited by convection electrons

We introduce the subwavelength transmission of an effective surface plasmon beyond the light zone via the proximity interaction of convection electrons with a metal grating. A comparative analysis of dielectric homogenization and a finite-difference-time-domain simulation shows that out-of-phase-like modes (pi modes) have strong transmission below the cutoff frequency relying on the parametric condition of structural dimension and electronic energy. The synchronous spatial field and charge distribution of the pi mode system confirms the evanescent tunneling effect of the electron-coupled plasmons.